CN113087629A - Preparation method of 1, 5-dichloro-2, 4-dinitrobenzene - Google Patents

Preparation method of 1, 5-dichloro-2, 4-dinitrobenzene Download PDF

Info

Publication number
CN113087629A
CN113087629A CN202110374481.2A CN202110374481A CN113087629A CN 113087629 A CN113087629 A CN 113087629A CN 202110374481 A CN202110374481 A CN 202110374481A CN 113087629 A CN113087629 A CN 113087629A
Authority
CN
China
Prior art keywords
temperature
dichloro
dinitrobenzene
feeding
stirring
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202110374481.2A
Other languages
Chinese (zh)
Inventor
李永祥
马忠平
梁栋
赵林秀
王艳红
胡志勇
李军
任福德
陈芳
陈丽珍
刘永政
张桐伟
刘文东
刘明
张帅
郑入水
霍媛媛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
North University of China
Original Assignee
North University of China
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by North University of China filed Critical North University of China
Priority to CN202110374481.2A priority Critical patent/CN113087629A/en
Publication of CN113087629A publication Critical patent/CN113087629A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06Preparation of nitro compounds
    • C07C201/08Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a preparation method of 1, 5-dichloro-2, 4-dinitrobenzene, which takes m-dichlorobenzene as a raw material, N-nitropyrazole and H2SO4Preparing 1, 5-dichloro-2, 4-dinitrobenzene for a nitrating agent; the method specifically comprises the following steps: taking 8ml of 98% sulfuric acid in a four-mouth bottle, mechanically stirring, dropwise adding 0.012mol of m-dichlorobenzene into concentrated sulfuric acid at the temperature of 20 ℃, heating in a water bath to 60 ℃ after feeding, uniformly adding 0.024mol of N-nitropyrazole in four parts at the temperature, wherein the reaction system is heated in the feeding process, feeding again after the temperature is reduced to the initial temperature, stirring after feeding is finished, reacting at the constant temperature of 65 ℃ for 6 hours, pouring the reaction solution into a container filled with ice blocks while the solution is hot, stirring to reduce the temperature of the solution to 5 ℃, and separating out solid suspended matters.

Description

Preparation method of 1, 5-dichloro-2, 4-dinitrobenzene
Technical Field
The invention relates to the field of compound preparation, and particularly relates to a preparation method of 1, 5-dichloro-2, 4-dinitrobenzene.
Background
The 1, 5-dichloro-2, 4-dinitrobenzene is mainly used as an intermediate for organic synthesis and also has application in auxiliaries, pesticides and medicines. 1, 5-dichloro-2, 4-dinitrobenzene has an important role in organic synthesis, the market of the product is always good, and the development of the product has good economic and social benefits.
At present, the 1, 5-dichloro-2, 4-dinitrobenzene is prepared by taking m-dichlorobenzene as a raw material and performing high-temperature nitration in a nitration system of mixed nitric acid and sulfuric acid. US005574188A discloses that the use of a fuming sulfuric acid-nitric acid system to nitrate 1, 3-dichlorobenzene gives an 89.8% yield; lepeng (Lepeng. preparation of intermediate RH1658 herbicide [ D ]. Shenyang university of industry, 2007.) in its Master paper 59.5g of m-dichlorobenzene was reacted at 110 ℃ for 3 hours by a mixed acid system of nitric and sulfuric acid at 100 ℃ with a reaction yield of 95%. However, the method has the disadvantages that the reaction temperature is high, and fuming nitric acid-concentrated sulfuric acid can generate a large amount of nitrogen oxide gas and excessive waste acid to cause environmental pollution.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of 1, 5-dichloro-2, 4-dinitrobenzene.
In order to achieve the purpose, the invention adopts the technical scheme that:
a process for preparing 1, 5-dichloro-2, 4-dinitrobenzene from m-dichlorobenzene as raw material and N-nitropyrazole and H2SO4Preparing 1, 5-dichloro-2, 4-dinitrobenzene for a nitrating agent; the method specifically comprises the following steps: taking 8ml of 98% sulfuric acid in a four-mouth bottle, mechanically stirring, dropwise adding 0.012mol of m-dichlorobenzene into concentrated sulfuric acid at the temperature of 20 ℃, heating in a water bath to 60 ℃ after feeding, uniformly adding 0.024mol of N-nitropyrazole in four parts at the temperature, wherein the reaction system is heated in the feeding process, feeding again after the temperature is reduced to the initial temperature, stirring after feeding is finished, reacting at the constant temperature of 65 ℃ for 6 hours, pouring the reaction solution into a container filled with ice blocks while the solution is hot, stirring to reduce the temperature of the solution to 5 ℃, and separating out solid suspended matters.
Further, the rotation speed of the mechanical stirring is 300-400 rpm.
The invention has the following beneficial effects:
the invention provides a preparation method of 1, 5-dichloro-2, 4-dinitrobenzene. According to the preparation method, N-nitropyrazole and sulfuric acid are used as nitration reagents, m-dichlorobenzene is directly nitrated to obtain 1, 5-dichloro-2, 4-dinitrobenzene, the raw material source is rich, the cost is low, the mixed acid of nitric acid and sulfuric acid is avoided being used as a nitrating agent, no pollution gas nitrogen oxide is generated in the reaction process, no waste acid is generated, and the environmental pollution is small; furthermore, the preparation method provided by the invention has the advantages that the nitration reaction is carried out at the temperature of 65 ℃, the reaction condition is mild, the long-time reaction at high temperature is not needed, the requirement on reaction equipment is low, the purification is easy, and the purity of the obtained product is high.
Drawings
FIG. 1 is a synthetic scheme of a process for preparing 1, 5-dichloro-2, 4-dinitrobenzene according to an embodiment of the present invention.
FIG. 2 is an infrared spectrum of the target product prepared in example 1 of the present invention.
FIG. 3 is a high performance liquid chromatography of the target product prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The embodiment of the invention provides a preparation method of 1, 5-dichloro-2, 4-dinitrobenzene, wherein m-dichlorobenzene is taken as a raw material, N-nitropyrazole and H2SO41, 5-dichloro-2, 4-dinitrobenzene is prepared for a nitrating agent, and the synthetic route is shown in figure 1; the method specifically comprises the following steps: taking 8ml of 98 percent sulfuric acid into a four-mouth bottle, dropwise adding 0.012mol of m-dichlorobenzene into concentrated sulfuric acid under the condition of mechanical stirring (300 plus 400 rpm) at 20 ℃, heating to 60 ℃ in a water bath after feeding, adding 0.024mol of N-nitropyrazole in batches at the temperature (the reaction system can be heated in the feeding process, and feeding is carried out again after the temperature is reduced to the initial temperature), keeping stirring after feeding, reacting at the constant temperature of 65 ℃ for 6h, pouring the reaction solution into a container filled with ice blocks while the solution is hot, stirring to reduce the temperature of the solution to 2 ℃, separating out solid suspended matters, refining by using ethanol after suction filtration and water washing, wherein the yield is 50.6 percent, the melting point of the product is measured by an X-4B micro melting point instrument: 101-103 ℃ (article value 101-104 ℃). The product is judged to be 1, 5-dichloro-2, 4-dinitrobenzene.
Table 1 results of elemental analysis of the target product of example one
The target product was subjected to elemental analysis and found to be 1, 5-dichloro-2, 4-dinitrobenzene as shown in Table 1, which showed that the measured values and the calculated values were substantially matched.
TABLE 1 elemental analysis results of the target products
Figure BDA0003010615770000031
FIG. 2 is an infrared spectrum of the target product prepared in example 1, with the following data:
IR(KBr,v cm-1)3088cm-1、1411cm-1there are absorption peaks, which indicate the presence of benzene ring, 900, 887, 818m-1Is the peak position of C-Cl; at 1571cm-1、1322cm-1Has strong absorption peak, and is proved to have C-NO2Is present.
FIG. 3 is a high performance liquid chromatography of the target product prepared in example 1 of the present invention;
chromatographic conditions are as follows: preparing solution containing target substance with acetonitrile and 0.1% acetic acid at flow rate of 1.0 mL/min-1The ultraviolet absorption wavelength is 260nm, and the sample injection amount is 20 mu L. As shown in FIG. 3, the retention time of the target product was about 11.22min, and the purity of the product was 98.5% by area normalization.
In summary, the molecular structure of the measured target product is consistent with the molecular structure of m-nitrochlorobenzene, that is, the target product obtained in the embodiment 1 of the present invention is m-nitrochlorobenzene, and the purity of the product is 98.5%.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.

Claims (3)

1. A preparation method of 1, 5-dichloro-2, 4-dinitrobenzene is characterized by comprising the following steps: using m-dichlorobenzene as raw material, N-nitropyrazole and H2SO4Preparing 1, 5-dichloro-2, 4-dinitrobenzene by using the nitrating agent.
2. The process for the preparation of 1, 5-dichloro-2, 4-dinitrobenzene according to claim 1, wherein: the method specifically comprises the following steps: taking 8ml of 98% sulfuric acid in a four-mouth bottle, mechanically stirring, dropwise adding 0.012mol of m-dichlorobenzene into concentrated sulfuric acid at the temperature of 20 ℃, heating in a water bath to 60 ℃ after feeding, uniformly adding 0.024mol of N-nitropyrazole in four parts at the temperature, wherein the reaction system is heated in the feeding process, feeding again after the temperature is reduced to the initial temperature, stirring after feeding is finished, reacting at the constant temperature of 65 ℃ for 6 hours, pouring the reaction solution into a container filled with ice blocks while the solution is hot, stirring to reduce the temperature of the solution to 5 ℃, and separating out solid suspended matters.
3. The process for the preparation of 1, 5-dichloro-2, 4-dinitrobenzene according to claim 2, wherein: the rotation speed of the mechanical stirring is 300-400 rpm.
CN202110374481.2A 2021-04-07 2021-04-07 Preparation method of 1, 5-dichloro-2, 4-dinitrobenzene Pending CN113087629A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110374481.2A CN113087629A (en) 2021-04-07 2021-04-07 Preparation method of 1, 5-dichloro-2, 4-dinitrobenzene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110374481.2A CN113087629A (en) 2021-04-07 2021-04-07 Preparation method of 1, 5-dichloro-2, 4-dinitrobenzene

Publications (1)

Publication Number Publication Date
CN113087629A true CN113087629A (en) 2021-07-09

Family

ID=76674780

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110374481.2A Pending CN113087629A (en) 2021-04-07 2021-04-07 Preparation method of 1, 5-dichloro-2, 4-dinitrobenzene

Country Status (1)

Country Link
CN (1) CN113087629A (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102173993A (en) * 2011-03-09 2011-09-07 南通市天时化工有限公司 Method for synthesizing 4,6-diamino resorcinol dihydrochloride (DAR)
WO2012088190A1 (en) * 2010-12-20 2012-06-28 E. I. Du Pont De Nemours And Company 2,4,5-triaminothiophenols and related compounds
CN110627738A (en) * 2019-10-23 2019-12-31 浙江南郊化学有限公司 Synthetic method of pesticide intermediate for synthesizing flumioxazin

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012088190A1 (en) * 2010-12-20 2012-06-28 E. I. Du Pont De Nemours And Company 2,4,5-triaminothiophenols and related compounds
CN102173993A (en) * 2011-03-09 2011-09-07 南通市天时化工有限公司 Method for synthesizing 4,6-diamino resorcinol dihydrochloride (DAR)
CN110627738A (en) * 2019-10-23 2019-12-31 浙江南郊化学有限公司 Synthetic method of pesticide intermediate for synthesizing flumioxazin

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GEORGE A. OLAH,ET AL.: "Aromatic Substitution. 47. Acid-Catalyzed Transfer Nitration of Aromatics with N-Nitropyrazole, a Convenient New Nitrating Agent", 《JOURNAL OF ORGANIC CHEMISTRY》 *
刘殿卿 等: "普莱克尼啶中间体9-甲基-2,4-二硝基-5-氯吖啶的合成", 《化学研究与应用》 *

Similar Documents

Publication Publication Date Title
CN112010856B (en) Folic acid telescoping process method by utilizing microchannel reaction
CN114349674A (en) Thiourea compound and preparation method thereof
US4952733A (en) Preparation of 1,3,5-triamino-2,4,6-trinitrobenzene from 3,5-dichloranisole
CN113087629A (en) Preparation method of 1, 5-dichloro-2, 4-dinitrobenzene
CN113072450A (en) Preparation method of m-nitrochlorobenzene
CN109180501B (en) Synthetic method of 4, 4' -diaminodiphenyl ether
CN112939867A (en) Preparation method of 4-nitropyrazole
CN112778351B (en) Preparation method of beta-dimethylphenyl silicon substituted aromatic nitro compound
CN112299952B (en) Method for producing 3-chloro-1, 2-propanediol by using acetic anhydride modified graphene oxide
CA1118770A (en) Process for the preparation of 6-demethyl-6-deoxy-6-methylenetetracyclines
CN114133373A (en) Method for synthesizing precursor of vilanterol intermediate
CN115772105B (en) Synthesis method of 4-nitroanisole
US20200140372A1 (en) Method for preparing nitrate ester
US3711552A (en) Process for the manufacture of n,n-bis-(2-chloroethyl)-2-nitro-4-alkylaniline
Kornblum et al. Substitution reactions which proceed via radical-anion intermediates. 31. Electron-transfer substitution reactions: stereochemistry
CN112062731A (en) Synthesis method of 1-phenyl-5-mercapto tetrazole
US4997987A (en) Preparation of 1,3,5-triamino-2,4,6-trinitrobenzene from 3,5-dichloroanisole
CN113149843B (en) Method for preparing 1,3,5-trinitrobenzene
CN113061113A (en) Preparation method of 4-nitroimidazole
CN109970701B (en) By using I2O5/NaNO2Process for nitrating electron-rich aromatic compounds
CN111875531B (en) Method for preparing 3-nitropyrrole based on sodium peroxodisulfate
CN113372255B (en) Method for synthesizing 2-substituted indole derivative under catalysis of copper
CN118724723A (en) Green synthesis method of nitrobenzene compounds
CN118652198A (en) Synthesis method and application of renewable energy source induced urea
US3093679A (en) Estervinylation of aromatic amines

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20210709